CN1239780C - Cellulose ethers and method of preparing same - Google Patents
Cellulose ethers and method of preparing same Download PDFInfo
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- CN1239780C CN1239780C CN00807877.7A CN00807877A CN1239780C CN 1239780 C CN1239780 C CN 1239780C CN 00807877 A CN00807877 A CN 00807877A CN 1239780 C CN1239780 C CN 1239780C
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
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Abstract
The present inventors have discovered that the solution rheology of cellulose ethers prepared from cellulose pulp is altered by mercerizing and recovering cellulose pulp before preparing the cellulose ethers. For example, the solution viscosity of carboxymethyl cellulose (CMC) produced from mercerized and recovered cellulose pulp is significantly greater than that produced from non-mercerized cellulose pulp. The present invention provides a method of preparing cellulose ethers comprising the steps of (a) obtaining mercerized and recovered cellulose pulp, and (b) converting the mercerized and recovered cellulose pulp into the cellulose ethers. The mercerized cellulose pulp is typically substantially free of cellulose III. Mercerized cellulose pulp prepared by this method has a greater percentage of crystalline cellulose II and a smaller crystalline area than that of non-mercerized cellulose pulp. The present invention also provides a method of preparing a cellulose floc comprising the steps of (a) obtaining mercerized and recovered cellulose pulp, and (b) treating the mercerized pulp to form the cellulose floc. Alternatively, the method comprises mercerizing and recovering a cellulose floc. Cellulose floc prepared by this method have a greater bulk density than cellulose floc prepared from similar non-mercerized cellulose pulp. Furthermore, the bulk density gain is greater than that expected from the coarseness (weight per unit of fiber length) gain from preparing a cellulose floc.
Description
Invention field
The method that the present invention relates to cellulose ether and prepare cellulose ether by the cellulose pulp of mercerization and recovery.The invention still further relates to: the cellulose pulp preparation according to mercerization and recovery has the method for the cellulose wadding condensate that increases bulk density.
Background of invention
Cellulose ether is at thickener (for example food additives); binding agent (for example lacquer and other colored paint), adhesive, printing base China ink; suspension stabiliser; thermoplastic, protecting colloid, emulsion stabilizer; finish composition (for example being used for textiles); coating composition (for example being used for paper and paper product), plastic sheet (for example being used for packing or textiles), and there is purposes widely the film forming agent aspect.For example, referring to: polymer science and engineering encyclopedia (the 2nd edition, 1985, John Wiley﹠amp; Sons, New York), the poromerics (Cellualr Materials to Composites) (the 3rd volume, " cellulose ether " chapter, 226-269 page or leaf) that is used for composite.Many high relatively viscosity of cellulose ether (fluid for example recovers the oil) that have benefited from during these are used.Before the present invention; the solution viscosity of cellulose ether mainly increases by the degree of polymerization (DP) or the viscosity of the cellulose slurry by being used to prepare cellulose ether, perhaps by protection DP during grinding at slurry or viscosity does not reduce and other treating method of carrying out during the cellulose ether preparation increases.
For example, have specific solution viscosity, so at first determine the viscosity of suitable cellulose slurry and the cellulose slurry that selection has this viscosity if wish cellulose ether.The selection strategy of this raw material is also adopted by the producer of ether, thereby by using more highdensity cellulose wadding condensate to increase output.
Usually, by make the cellulose alkalization with basifier such as NaOH, to form alkali cellulose; Make the alkali cellulose etherificate then and produce cellulose ether.For example, referring to US2,067,946; 2,636,879; 4,063,018; 4,250,305; 4,339,573; With 4,547,570.Before alkalization, cellulose slurry can be shortened or grinds to form the cellulose wadding condensate.For example, referring to US2,067,946; 2,636,879; With 4,339,573.
People's such as Edelman US4,941,943 have disclosed a kind of preprocess method that is used to prepare carboxymethyl cellulose.This preprocess method comprises: with cellulose dash slurry into about the denseness of 5-15% to form fibrous suspension, the denseness that fibrous suspension is concentrated into about 25-35% makes this slurry homogenising then with the formation slurry.After fibrous suspension concentrates, make this slurry mercerization to form activated cellulose (or alkali cellulose).The mercerization step can be before the homogenising step, afterwards or adverse current carry out.After preprocessing process, make the activated cellulose etherificate become sodium carboxymethylcellulose.
People's such as Orii US4,292,426 have disclosed the preparation method of hydroxypropyl cellulose.This method need make the cellulose swelling, discharges excessive sodium hydroxide solution from the cellulose of swelling, thereby forms hydrate cellulose; And by with sodium hydrate aqueous solution to the washing of hydrate cellulose and the dry alkali cellulose that obtains.Alkali cellulose is washed so that reduce the alkali content of hydrate cellulose.Final alkali cellulose, its NaOH and cellulosic ratio from 0.05 to 0.16, water is to cellulosic ratio from 0.2 to 0.5.This method also comprises in addition: make the reaction of alkali cellulose and propylene oxide, until molar substitution till between 1 and 2; For every part of cellulose in the raw material alkali cellulose, add 0.2-0.7 part water; And proceed etherification reaction, till molar substitution is greater than 2.5.
People's such as Bredereck US4,491,661 have disclosed a kind of preparation method of water-soluble cellulose ether, comprise: utilize ammoniacal liquor to make cellulose activation, in the presence of ammoniacal liquor, utilize basifier to make the activated cellulose alkalization, in the presence of basifier, from the alkalization cellulose, remove ammoniacal liquor, and in the presence of organic solvent, utilize etherifying agent to make the alkali cellulose etherificate.When making cellulose activation, will form avicel cellulose III by liquefied ammonia.Just as known in the art, avicel cellulose III and other avicel cellulose structure, II compares as avicel cellulose, has visibly different structure and performance.For example, referring to above-mentioned Rydholm; And above-mentioned Ott, Spurlin and Grafflin are described.
People's such as Laskowksi DDR146,462 have disclosed a kind of substitution value is lower than 0.5 the cellulosic preparation method of low replacement, water-soluble carboxymethyl.This method comprises: utilize liquefied ammonia to make cellulose activation, evaporate ammonia, utilize NaOH to make the activated cellulose alkalization, and make the carboxymethyl celluloseization of alkalization.
People's such as Dautzenberg DDR148,342 have disclosed a kind of preparation method with the carboxymethyl cellulose that increases solution viscosity.This method comprises: utilize liquefied ammonia to make cellulose activation, make the activated cellulose alkalization, and make the carboxymethyl celluloseization of alkalization.
At present, need a kind of preparation method who increases the cellulose ether of output, and wherein the solution viscosity of cellulose ether can be controlled, and be not the viscosity of raw material by treatment conditions.In addition, also need a kind of preparation method of cellulose wadding condensate, this method will increase the bulk density of every number average flocculate length.
Brief summary of the invention
The present invention finds, the rheology of solution of the cellulose ether that makes by cellulose slurry, and the mercerization by making cellulose slurry before this cellulose ether preparation and reclaiming changes.For example, also the solution viscosity of the carboxymethyl cellulose (CMC) of the cellulose slurry production of recovery will be obviously greater than the solution viscosity of being starched the carboxymethyl cellulose (CMC) of production by non-mercerized cellulose by mercerization.
The invention provides a kind of preparation method of cellulose ether, comprise the steps: the cellulose slurry that (a) obtains mercerization and reclaim, (b) make the cellulose slurry of mercerization and recovery change into cellulose ether, wherein using cellulose II mercerization agent that the cellulose paste of the mercerization in the step (a) is carried out mercerization handles, wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, and wherein said recovery comprises neutralization and/or washing.When cellulose slurry was southern softwood kraft pulp, the TAPPI 230 om-89 viscosity numbers of mercerized cellulose slurry will be greater than 12cP.This mercerized cellulose is starched usually not cellulose III.Compare with non-mercerized cellulose slurry by the mercerized cellulose slurry that this method makes, have the avicel cellulose II of higher percentage and crystal region still less.
According to embodiment preferred, described method comprises: (a) cellulose slurry that obtains mercerization and reclaim, (b) cellulose slurry of mercerization and recovery is handled to form the cellulose wadding condensate, (c) the cellulose wadding condensate is alkalized into alkali cellulose, the alkali cellulose etherificate is become cellulose ether with (d).When cellulose slurry was southern softwood kraft pulp, the TAPPI 230om-89 viscosity number of mercerized cellulose slurry will be greater than 12cP.According to another embodiment, put upside down with step (a) with (b), be about to cellulose slurry and be processed into the cellulose wadding condensate, then the cellulose wadding condensate is carried out mercerization and recovery.
In addition, the present invention also provides a kind of preparation method of cellulose wadding condensate, comprise the steps: the cellulose slurry that (a) obtains mercerization and reclaim, and (b) mercerization slurry is handled to form the cellulose wadding condensate, mercerization and the cellulose slurry that reclaims cellulose III not wherein, and wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.When cellulose slurry was southern softwood kraft pulp, the TAPPI 230 om-89 viscosity numbers of mercerized cellulose slurry will be greater than 12cP.In addition, this method comprises that also the cellulose wadding condensate is carried out mercerization also to be reclaimed.By the cellulose wadding condensate that this method makes, wherein bulk density is greater than the bulk density of the cellulose wadding condensate that is made by similar non-mercerized cellulose slurry.In addition, the bulk density value added increases desired bulk density greater than the roughness (weight of per unit fibre length) that is caused by the preparation of cellulose wadding condensate increases.
More specifically, the invention provides a kind of preparation method of mercerized cellulose flocculate, comprise the steps: that (a) makes the mercerization of cellulose wadding condensate; (b) reclaim the mercerized cellulose flocculate, wherein, the cellulose wadding condensate of mercerization and recovery is cellulose III not, and wherein the cellulose wadding condensate of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose wadding condensate and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.
Another embodiment is the preparation method of cellulose ether, comprises the steps: that (a) selection is used for the viscosity of the hope of cellulose ether, (b) cellulose slurry that obtains mercerization and reclaim, and this slurry has the suitable viscosity of the cellulose ether that obtains selected viscosity; (c) cellulose slurry with mercerization and recovery changes into cellulose ether, wherein, the cellulose slurry of mercerization and recovery is cellulose III not, and wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, during described recovery comprises and/or the washing.When cellulose slurry was southern softwood kraft pulp, the TAPPI 230 om-89 viscosity numbers of mercerized cellulose slurry will be greater than 12cP.
Summary of drawings
Fig. 1 is the line graph of the dried flocculate density of the cellulose wadding condensate that made by mercerization and non-mercerization south softwood kraft pulp north needlebush sulfite pulp and cotton linter pulp to the flocculate number average fiber length.
Fig. 2 is the mercerization cotton linter pulp, southern softwood kraft pulp, the line graph of the percentage of the NaOH that the Rx value of northern needlebush sulfite pulp and southern broad-leaved wood sulphate pulp applies during to pulp processing.
Detailed Description Of The Invention
Be surprisingly found out that the cellulose ether that the cellulose slurry that is also reclaimed by previous mercerization makes is compared with the similar cellulose ether that is made by non-mercerized cellulose slurry, has visibly different rheology of solution. For example, the viscosity of prepared cellulose ether can be by changing technological parameter as being controlled by changing the mercerization degree. Therefore, the producer can utilize the cellulose slurry of identical type, and for example southern softwood kraft pulp (SSK), and treatment facility obtains the cellulose ether of wide region rheology of solution, and need not to change the kind of cellulose slurry or treatment facility. For some cellulose ether, such as carboxymethyl cellulose, the cellulose slurry that mercerization is also reclaimed is used as raw material, will obviously increase the solution viscosity of cellulose ether. The increase of solution viscosity provides such chance to the cellulose ether producer, namely can compete with synthetic and other natural water-soluble copolymer of wide region, can develop the new purposes of cellulose ether, and improve the performance of present product.
The inventor finds that also the cellulose wadding condensate that the cellulose slurry that is also reclaimed by mercerization makes is more tightr than the cellulose wadding condensate that is made by non-mercerized cellulose slurry. Term " cellulose wadding condensate " is defined as used herein: the fibre length by cellulose slurry shortens resulting material, shreds, shears or grind to form shorter length with sheet material or bulky material and have nothing to do. The increase of flocculate density is so that the cellulose ether producer can increase the output of pulp mill. As shown in Figure 1, cotton linter pulp (CLP), south softwood kraft pulp (SSK), mercerization fiber with northern needlebush sulfite pulp (NSS), compare with its non-mercerized cellulose slurry, all have higher flocculate density, this and flocculate (fiber) length have nothing to do. For example, the cellulose wadding condensate of grinding, the bulk density of its flocculate is usually than the about 20-60% of similar flocculate that is obtained by non-mercerized cellulose slurry. This density contrast all will provide obvious advantage aspect reactor useful load and the ether product output.
The preparation of the cellulose slurry of mercerization and recovery
Mercerization and the cellulose slurry that reclaims can make the cellulose slurry mercerization by (i), (ii) washing, neutralization, or washing and in and the mercerized cellulose slurry, and (iii) non-mandatorily mercerized cellulose is starched and is carried out drying and prepare.
Any cellulose slurry known in the art all can be used as raw material. Suitable cellulose slurry source is including, but not limited to cotton linter pulp, broad-leaved wood fiber element slurry (for example broad-leaved wood sulphate pulp), needle-leaved wood fibre element slurry (for example softwood kraft pulp), sulfite cellulose slurry (for example needlebush and leaf wood sulfite pulp) sulphate cellulose slurry, rehydration cellulose slurry, and any combination of aforementioned fibers element slurry. Suitable broad-leaved wood fiber element slurry is including, but not limited to southern hemisphere leaf wood sulphate cellulose slurry, south hemisphere leaf wood sulfite cellulose slurry, this may be starched by ground Na Weiya (Scandavian) leaf wood sulphate cellulose, this may be starched by ground Na Weiya leaf wood sulfite cellulose, north leaf wood sulphate cellulose slurry (NHK), north leaf wood sulfite cellulose slurry, south leaf wood sulphate cellulose slurry (SHK), south leaf wood sulfite cellulose slurry, torrid zone leaf wood sulphate cellulose slurry, torrid zone leaf wood sulfite cellulose slurry, and any combination of aforementioned slurry. Suitable needle-leaved wood fibre element slurry is including, but not limited to southern hemisphere needlebush sulphate cellulose slurry, south hemisphere needlebush sulfite cellulose slurry, this may be starched by ground Na Weiya needlebush sulphate cellulose, this may be starched by ground Na Weiya needlebush sulfite cellulose, south needlebush sulphate cellulose slurry (SSK), north needlebush sulphate cellulose slurry (NSK), south needlebush sulfite cellulose slurry (SSK), north needlebush sulfite cellulose slurry (NSS), and any combination of aforementioned slurry. Suitable sulfite cellulose slurry is including, but not limited to southern needlebush sulfite cellulose slurry, northern needlebush sulfite cellulose slurry, tropical leaf wood sulfite cellulose slurry, and any combination of aforementioned slurry. The slurry that can mention especially is cotton linter pulp, needlebush sulfite cellulose slurry, and do not have the dry cellulose slurry of crossing.
Cellulose slurry can be the mixture of two or more different cellulose slurries. Preferably, described cellulose slurry is not the regenerated cellulose slurry. Be applicable to sulphate cellulose slurry of the present invention and can carry out or not carry out prehydrolysis. In addition, described cellulose slurry can be any cellulose wadding condensate of previous materials.
Cellulose slurry can carry out mercerization by any method known in the art, the pulping process of editing at Rydholm (Interscience Publishers for example, 1965) and Ott, cellulose that Spurlin and Grafflin edit and cellulose derivative (V volume, part 1, Interscience Publishers, 1954) the middle method of describing, be introduced into as a reference at this.The mercerization effect is that cellulose I changes into form more stable on the thermodynamics, i.e. cellulose II with cellulose from its native form.Cellulose slurry can react and mercerization by making slurry and mercerization agent, and described mercerization agent is as changing into cellulose the mercerization agent (being the mercerization agent of cellulose II) of cellulose II from cellulose I.According to an embodiment preferred, the mercerization agent is not ammonia or amine.
Suitable mercerization agent is including, but not limited to alkali metal hydroxide, as NaOH (NaOH), and lithium hydroxide (LiOH), potassium hydroxide (KOH), and rubidium hydroxide (RbOH); Benzyltrimethylammonium hydroxide (BTMOH); And aforementioned combination arbitrarily.
According to embodiment preferred, the mercerization agent is a NaOH.Usually, cellulose slurry is used based on total aqueous solution meter of 100% weight and is preferably handled from the sodium hydrate aqueous solution of about 7-24% weight from about 6.5-50%.This is equivalent to concentration sodium hydroxide and the concentration sodium hydroxide from about 75 grams to about 300 grams every liter (g/l) from about 70 grams to about 764 grams every liter (g/l) respectively.Usually, utilize the mercerization agent,, under agitation cellulose slurry is handled in about 20 ℃ or higher temperature.The mercerization effect can be carried out during the slurry production process or afterwards, is included between boiling, bleaching, purification and dry period and afterwards.In addition, mercerization step also can be carried out during the rehydration cellulose slurry.According to embodiment preferred, mercerization is carried out during acting on the bleaching of slurry production period and/or purification processes.
According to embodiment preferred, mercerization acts under the oxygen-free substantially environment, carries out under in blanket of nitrogen.Oxygen will destroy polymer chain, and cause more low viscous end product.
The mercerization effect is carried out at the environment product that do not contain etherifying agent substantially usually, more preferably, based on the gross weight of cellulose slurry and etherifying agent 100%, carries out in comprising the environment that is lower than about 0.1% weight etherifying agent.Most preferably, carrying out the mercerization effect without any in the presence of the etherifying agent.
After the mercerization effect, in cellulose slurry crystalline portion 100% gross weight, cellulose slurry preferably comprises at least about 20%, more preferably at least about 35%, and the cellulose II of 60% weight most preferably from about.Usually, crystalline portion only is made up of cellulose I and cellulose II.
Then, the plain slurry of recycled fiber from cellulose slurry and mercerization agent, i.e. most or all mercerization agent in recovery or the neutralise mixt.Usually, mercerized cellulose slurry is washed and/or neutralize.For example, can water, weak acid (for example acid of pH from about 4.0 to about 6.9), the solution of weak mercerization agent (for example, the solution of pH from about 7.1 to about 10.0), or aforementioned combination arbitrarily wash the mercerization slurry.
In addition, also can be by neutralizer being added in the cellulose slurry and in and the mercerization agent.Suitable neutralizer is including, but not limited to sulfuric acid, hydrochloric acid, oxalic acid, sulfur dioxide, phosphoric acid and aforementioned combination arbitrarily.Cellulose slurry can wash and neutralizes with any order.Usually, slurry is neutralized to about 6.0 to about 8.0 pH value.After the cellulose slurry neutralization, preferably wash, to remove excessive salt, as sodium chloride (NaCl).The mercerization agent can be reclaimed during washing and/or neutralization procedure, and recycles subsequently.
According to embodiment preferred, mercerized cellulose slurry water washs.Usually, mercerized cellulose slurry water washs, be lower than until the pH value of the residual water of slurry about 10.0, preferably from about 5.0 to about 8.0.
In cellulose slurry and mercerization agent 100% weight, the cellulose slurry of washing and/or neutralization comprises the mercerization agent that is lower than about 3.5% weight usually.In cellulose slurry and mercerization agent 100% weight, the cellulose slurry of washing and/or neutralization comprises usually and is lower than approximately 0.3%, more preferably less than about 0.03%, most preferably is lower than the mercerization agent of about 0.02% weight.
Cellulose slurry can carry out drying after mercerization and washing and/or neutralization procedure, so that produce sheet material, and bale packing, or the plain slurry of loose fibres.Drying can be carried out with any method known in the art.Preferably, in plain slurry of total fiber and water 100% weight, cellulose slurry is dried to: cellulose slurry comprises and is lower than approximately 20%, more preferably less than about 15%, most preferably is lower than the moisture content of about 10% weight.Drying at about 100 to about 185 ℃, is preferably carried out to about 170 ℃ temperature about 120 usually.
Preferably, with alkali metal hydroxide mercerization and the cellulose slurry such as the CLP that reclaim, NSS, SSK and SHK, its Rx value is greater than about 0.57, more preferably greater than about 0.60, most preferably greater than about 0.64.Preferably, mercerization and the cellulose slurry that reclaims, in plain 100% weight of total fiber, it is about 60% that its overall crystallinity is lower than, more preferably less than the crystalline portion of about 50% weight.Mercerization and the lignocellulose slurry that reclaims, in plain 100% weight of total fiber, its overall crystallinity is lower than the crystalline portion of about 45% weight.
According to embodiment preferred, in the plain slurry of total fiber 100% weight, mercerization and the CLP that reclaims, its Rx value greater than about 0.57 and its overall crystallinity be lower than about 60% weight.According to another embodiment preferred, in the plain slurry of total fiber 100% weight, mercerization and the SHK that reclaims, its Rx value greater than about 0.57 and its overall crystallinity be lower than about 50% weight.According to another embodiment preferred, in the plain slurry of total fiber 100% weight, mercerization and the SSK that reclaims, its Rx value greater than about 0.57 and its overall crystallinity be lower than about 50% weight.According to another embodiment preferred, in the plain slurry of total fiber 100% weight, mercerization and the NSS that reclaims, its Rx value greater than about 0.57 and its overall crystallinity be lower than about 50% weight.
When cellulose slurry is southern softwood kraft pulp, mercerization and the cellulose slurry that reclaims, when measuring by TAPPI T230 om-89, its viscosity number is at least 12cP usually.Preferably, when measuring by TAPPI T230 om-89, the viscosity number of the southern needlebush sulphate cellulose slurry of mercerization is at least 20cP usually, more preferably is at least 26cP.
Preferably, mercerization and the cellulose slurry that reclaims cellulose III not substantially.In cellulose slurry crystalline portion 100% gross weight, the cellulose slurry of mercerization preferably comprise be lower than about 20%, more preferably less than the cellulose III of about 5% weight.
Usually, mercerization and the cellulose slurry that reclaims do not contain etherifying agent substantially, and in the gross weight of cellulose slurry and etherifying agent 100%, preferably comprise the etherifying agent that is lower than about 0.1% weight.More preferably, the cellulose slurry of mercerization and recovery does not contain etherifying agent.
Preferably, mercerization and the cellulose slurry that reclaims are previously prepared, promptly prepare in the place away from a large amount of preparation cellulose ethers.Term " in a large number " is defined as the amount greater than about 200kg as used herein.
The preparation of cellulose wadding condensate
Before or after mercerization and reclaiming slurry, cellulose slurry can be changed into the cellulose wadding condensate.Preferably, before changing into the cellulose wadding condensate, make cellulose slurry carry out mercerization and recovery.
The cellulose wadding condensate can be produced by any method known in the art, as passes through mechanical treatment process.Cellulose slurry can grind, and is ground to the flocculate size of hope as the cut-off blade that utilizes rotation.In addition, also can utilize one-level and/or secondary rotating knife that cellulose slurry is ground.In addition, slurry can or cut into the cellulose wadding condensate by the methods known in the art chopping.
The fibre length of the plain flocculate of milled fibre can change according to the ether of producing.Number average flocculate length, promptly the length of fiber changes to about 2.0 millimeters scopes about 0.1 in the flocculate.The preferred fibre length that is used for the plain flocculate of milled fibre is from about 0.2 to about 0.5 millimeter.The flocculate length of chopping is usually from about 0.5 to about 5.0 millimeters, preferably from about 1 to about 3 millimeters.The dry density of flocculate mainly changes according to the length of flocculate and the density of mercerized cellulose slurry.
For example, number average flocculate length is the cellulose wadding condensate that 0.25 to 0.50 millimeter CLP of the present invention derives and obtains, and its flocculate bulk density is as described below:
The flocculate bulk density
The CLP flocculate=m* (AFL)
-0.8043
M is from 0.0755-0.0835 in the formula, and AFL represents number average flocculate length.Number average flocculate length is the cellulose wadding condensate that 0.25 to 0.50 millimeter SSK of the present invention derives and obtains, and its flocculate bulk density is as described below:
The flocculate bulk density
The SSK flocculate=m* (AFL)
-0.9676
M is from 0.0841-0.0925 in the formula, and AFL represents number average flocculate length.Number average flocculate length is the cellulose wadding condensate that 0.25 to 0.50 millimeter NSS of the present invention derives and obtains, and its flocculate bulk density is as described below:
The flocculate bulk density
The NSS flocculate=m* (AFL)
-0.7336
M is from 0.0689-0.0758 in the formula, and AFL as mentioned above.
The preparation of cellulose ether
The mercerized cellulose slurry can change into cellulose ether by any known method in this area.The method for optimizing that transforms the mercerized cellulose slurry comprises: the mercerized cellulose slurry is handled with formation cellulose wadding condensate, and the cellulose wadding condensate is changed into cellulose ether.For example, can be by the cellulose wadding condensate being alkalized forming alkali cellulose, and the alkali cellulose etherificate is become cellulose ether, and the preparation cellulose ether.Can prepare the cellulose wadding condensate as mentioned above or by any method known in the art.In addition, also can under the situation that does not form the cellulose wadding condensate, prepare cellulose ether by alkalization and ether to cellulose slurry.
In addition, can carry out mercerization and recovery to the cellulose wadding condensate as mentioned above, change into cellulose ether then.For example, alkalize with the formation alkali cellulose, and alkali cellulose is carried out etherificate by cellulose wadding condensate to mercerization and recovery, and the preparation cellulose ether.
The alkalization of mercerized cellulose slurry/flocculate
Cellulose slurry or flocculate can alkalize by any method known in the art.For example, cellulose slurry or flocculate can be used alkali metal hydroxide, handle as NaOH, so that form alkali cellulose.Suitable alkali metal hydroxide including, but not limited to recited above those.Alkali metal hydroxide and fibrin reaction will destroy in the cellulose chain intermolecular hydrogen bonding and destroy the cellulosic active crystal region of owing.
Usually, mercerized cellulose is handled with the aqueous solution, and in the aqueous solution 100% gross weight, the described aqueous solution comprises about 15 to about 80%, preferably from about 25 to about 65%, more preferably from about 30 alkali metal hydroxides to about 50% weight.Alkalinization at about 20 to about 40 ℃, is preferably carried out to about 34 ℃ temperature about 24 usually.
According to embodiment preferred, alkalinization is carried out under oxygen-free substantially environment, carries out under in blanket of nitrogen.Oxygen will destroy polymer chain, cause more low viscous end product.
The etherificate of alkali cellulose
Final step is the etherificate of alkali cellulose.Usually, make the alkali cellulose etherificate by the reaction that makes alkali cellulose and etherifying agent.Suitable etherifying agent is including, but not limited to halogenated acetic acids and salt thereof, as chloroacetic acid sodium.The whole bag of tricks that is prepared cellulose ether by alkali cellulose is described in US4, and 063,018; 4,250,305; With 4,547, in 570, be introduced into as a reference at this.
The cellulose wadding condensate is changed into alkali cellulose and etherification step can carry out simultaneously or sequentially.
Cellulose ether that can be by method of the present invention preparation is including, but not limited to ion-type and non-ionic celluloses ether.The example of described cellulose ether is including, but not limited to carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropyl cellulose (HPC), methyl hydroxyethylcellulose (MHEC), ethylhydroxyethylcellulose (EHEC), methylcellulose (MC), and methylhydroxypropylcellulose (MHPC).The cellulose ether that is made by method of the present invention is particularly suitable for as the raw material for preparing water-soluble polymer.
For example, this method can prepare: the carboxymethyl cellulose (CMC) that cotton linter pulp is derived and obtained, and in the aqueous solution that 1% weight CMC forms, according to ASTM D 2196, its solution viscosity is from about 60,000 to about 100,000cP; The CMC that softwood kraft pulp is derived and obtained, in the aqueous solution that 1% weight CMC forms, its solution viscosity is from about 1,000 to about 1,600cP; The CMC that broad-leaved wood sulphate pulp is derived and obtained, in the aqueous solution that 1% weight CMC forms, its solution viscosity is from about 1,000 to about 1,600cP; The CMC that wood pulp is derived and obtained, in the aqueous solution that 1% weight CMC forms, its solution viscosity from about 1,800 to about 3000cP; Preferred cotton linter pulp derive the CMC that obtains including, but not limited to: in the aqueous solution that 1% weight CMC forms, according to ASTM D 2196, its solution viscosity is from about 70,000 to about 85, those CMC of 000cP.Preferred softwood kraft pulp derive the CMC that obtains including, but not limited to: in the aqueous solution that 1% weight CMC forms, its solution viscosity is from about 1,100 to about 1, those CMC of 400cP.Preferred broad-leaved wood sulphate pulp derive the CMC that obtains including, but not limited to: in the aqueous solution that 1% weight CMC forms, its solution viscosity is from about 1,200 to about 1, those CMC of 400cP.Preferred wood pulp derive the CMC that obtains including, but not limited to: in the aqueous solution that 1% weight CMC forms, its solution viscosity is from about 2,000 to about 2, those CMC of 600cP.These viscosity numbers are according to ASTM D 2196, are measured by standard Brookfield viscosimeter (LVDV2+ type).Suitably select spindle size (2-4), to guarantee that torque is greater than 10 and less than 90.Spindle speed is arranged on 60rpm.For high viscosity CMC,, may need 4 spindle size and rotating speed is arranged on 6rpm, so that measure 1% viscosity in aqueous solution as the CMC that makes by mercerization CLP.
The cellulose ether that is made by method of the present invention can be used for preparation, water-soluble polymer for example, synthetic thickening agent; the oil recovery fluid, the auxiliary agent of preserving moisture, binding agent (for example lacquer and other colored paint); adhesive, printing base China ink, suspension stabiliser; thermoplastic, protecting colloid, emulsion stabilizer; film forming agent; finish composition (for example being used for textiles), coating composition (for example being used for paper and paper product), and plastic sheet (for example being used for packing or textiles).
The following examples will be illustrated the present invention and the present invention do not limited.Except as otherwise noted, all percentage number averages by weight.Term " (w/w) " is defined as: in the gross weight of mixture 100%, and the weight of one or more concrete compositions in the mixture.
Embodiment 1
The derive preparation of the cellulose wadding condensate that obtains of cotton linter pulp
Utilize the NaOH (NaOH) of 75g/L 7% (w/w), the NaOH of 111g/L 10% (w/w), the NaOH of 162g/L 14% (w/w), the NaOH of 216g/L 18% (w/w), in 25 ℃, undried cotton linter pulp sample is handled (3% denseness, 15 minutes).Each slurry sample was all bleached 50 minutes at 50 ℃ with hypochlorite.Then, slurry is washed and with sulfuric acid and oxalic acid slurry handled under 3.5% denseness, and (Alpharetta, Dynamique GA) copy the sheet machine and form sheet material by deriving from Cybermetrics.Sheet material carried out drying and utilizes Wiley Mill grinder (derive from Arthur H.ThomasCo., Philadelphia PA) grinds, and is 0.45 millimeter cellulose wadding condensate thereby form number average flocculate length (AFL).The number average fiber length of flocculate is to utilize KajaaniFS-200 fibre analysis instrument (derive from Neles/Valmet, Kajaani Finland) measures.
The viscosity of slurry and flocculate is measured according to TAPPI T230 om-89.
The bulk density of dried flocculate is to utilize the graduated cylinder of 250 millimeters scales, measures according to ASTM D 1439; Described graduated cylinder is equipped with flocculate and raps 1000 times so that simulate filling in reactor.
According to " slurry water conservation capacity (swelling value) measurement " (Theodor Hopner, Grorg Jaymeand Johannes C.Ulrich,
Das Papier, Vol 9, No.19/20, pp.476-482 (1955)) and the middle method of describing, measure the water retention value (WRV) of grinding flocculate.Usually, make again the slurry sample that divides in water swelling 16-24 hour, carry out centrifugal treating with 1500g then.Then the sample of wet centrifugal mistake is carried out steadyly, carry out drying at 105 ± 2 ℃, and steady once more.The moisture content of staying after centrifugal treating in the sample mainly is because commonly used the reservation.WRV determines according to following formula:
The weight of WRV=(weight of the weight-dry sample of wet centrifugal sample) * 100%/dry sample
Percentage of the cellulose II of cellulose slurry sheet material (in the weight of total crystallization part 100% weight) and degree of crystallinity (crystallinity Xc) (in the weight of plain 100% weight of total fiber) are by measuring (Teltow-Seehof with the wide-angle X-ray scattering (WAXS) of Fraunhofer-Institute of Applied Polymer Research, Germany, Fink, H.-P., Walenta, E. (1994), R ntgenbeugungsuntersuchungen zur ü bermolekulararen Struktur von Cellulose imVerarbeitungsproze β .Das Papier 12,739-748; H.-P, Fink, D.Hofmann, and B.Philipp, Cellulose 2 (1995), 51-70).Utilize the Siemens D-500 diffractometer that becomes symmetrical transmission configuration with Ge main beam monochromator (isotropism sample, 4 °≤2 θ≤104 °).
The following measurement of Rx value that is used for the sheet material slurry.The sheet material slurry is carried out X-ray diffraction (Philips PW 1729 x-ray generators that have the PW1840 diffractometer), so that determine the peak intensity of native cellulose I fiber and mercerized cellulose II fiber.The Rx value is the ratio of the peak diffraction of cellulose II to the peak diffraction summation of cellulose II and cellulose I.Referring to Raschand McCarthy, Norsk Skogindustri, 8:329,1954.The percentage of cellulose II increases along with the increase of Rx value.The intensity that the Rx value is shone by the diffraction at about 12.6 and 15.6 degree is derived and is obtained, and according to formula Rx=2I
12.6/2I
12.6+ I
15.6Calculate.
The results are shown among the following table 1A.
Table 1A
The effect of the sheet material that mercerization is derived to CLP and the performance of flocculate
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples (0%) | 7％ | 10％ | 14％ | 18％ |
| Sheet material viscosity (cP) | 277 | 267 | 262 | 218 | 224 |
| Flocculate viscosity (cP) | 202 | 206 | 198 | 172 | 166 |
| Average floc length (mm) | 0.45 | 0.45 | 0.44 | 0.45 | 0.45 |
| Flocculate density (g/mL) | 0.108 | 0.112 | 0.116 | 0.147 | 0.152 |
| Flocculate WRVs (%) | 56.5 | 54.5 | 55.2 | 65.6 | 65.9 |
| Sheet material Rx value | 0.5406 | 0.5370 | 0.5408 | 0.6341 | 0.6540 |
| Sheet material cellulose II (%) | 0 | 0 | 0 | 38 | 62 |
| Sheet material crystallinity Xc (%) | 61 | 60 | 61 | 52 | 46 |
The increase of the naoh concentration that uses in the mercerization agent is handled will make the viscosity of cotton linter pulp (CLP) reduce.Yet flocculate density will increase along with the increase of mercerization agent treating capacity.18% naoh treatment will cause CLP flocculate density to increase by 41% than Comparative Examples.
The derive preparation of the CMC that obtains of cotton linter pulp
Utilization derive from Janke and Kunkel (Staufen, IKA reactor Germany), as described below, flocculate is changed into carboxymethyl cellulose (CMC).40-50 gram (over dry) cellulose wadding condensate is soaked in the water spends the night.The cellulose that will soak is added in the 776-870 gram aqueous isopropanol (99.0%) then.The slurries that obtain were stirred 30 minutes at about 25 ℃.The sodium hydrate aqueous solution of 46-58 gram 50% (w/w) is added in these slurries, so that make the alkalization of cellulose wadding condensate.Alkalization was carried out 30 minutes at about 25 ℃.Be dissolved in the chloroacetic acid of 26-35 gram 99.6% in the 100 gram isopropyl alcohols and be added in the described slurries.Then, with slurries be heated to 75 ℃ carry out for the time 1.5 hours heating, then, stop reaction, and utilize the B ü chner funnel of the 15cm of band #4 filter paper to make the slurries drainage.Filter liquor methanol wash four times are to remove sodium chloride and other accessory substance.Then the CMC of remainder is carried out drying at about 55 ℃ with compressed air, and utilize standard step as described below and method (being the ASTM method) to assess.Prepare two independently CMC batch of materials and under each the mercerization agent agent concentration except that 7% and 10%, testing.Only preparing a CMC batch of material also tests under 7% and 10% mercerization agent concentration respectively.
According to ASTM D 2196, utilize standard Brookfield viscosimeter (LVDV2+ type), measure the ether rotary viscosity of the aqueous solution in 0.5% to 1% scope.Suitably select spindle size (2-4), to guarantee that torque is greater than 10 and less than 90.In table 1B, pointing out in addition, spindle speed is arranged on 60rpm.For the high viscosity CMC that makes by mercerization CLP, may need 4 spindle size and rotating speed is arranged on 6rpm, so that measure 1% viscosity in aqueous solution.
By ashing CMC sample (0.2-1.0) being carried out titration, and measure the substitution value (DS) of CMC with 0.1N hydrochloric acid.Prepared ashing CMC sample in about 20 minutes by CMC being heated at about 600 ℃.The DS value of CMC about 0.7 to about 0.85 scope.
The results are shown among the following table 1B.
Table 1B
Mercerization is to the derive effect of the CMC performance that obtains of CLP-
| Mercerization agent treating capacity (NaOH (w/w)) | CMC 0.50% viscosity (cP) | CMC 0.75% viscosity (cP) | CMC 1% viscosity (cP) * * | CMC substitution value (DS) |
| Comparative Examples (0%) | 754 | 2751 | 34690 | 0.825 |
| 7％ | 825 | 2538 | 40600 | 0.765 |
| 10％ | 742 | 2373 | 35450 | 0.846 |
| 14％ | 1678 | 4889 | 80095 | 0.729 |
| 18％ | 1713 | 6387 | 83745 | 0.794 |
* utilizes the viscosity of #4 spindle with spindle tachometric survey 1% solution of 6rpm.
Add mercerization agent processing section and can not improve the substitution value (DS) of CMC solution.Yet, will improve (the CMC solution for 0.75% is 78% during 14% (w/w) NaOH, and is 132% during 18% (w/w) NaOH) greatly by the CMC solution viscosity that naoh treatment caused.
Embodiment 2
Cellulose wadding condensate that south softwood kraft pulp (SSK) is derived and the preparation of CMC
Utilization is set to 600 counter, according to the method for describing among the TAPPI TMI 73-06-00, makes that (Foley, non-mercerization SSK pulpboard (E30 level) FL) decomposes, thereby forms slurries from Buckeye Technolohies.Then, utilize the NaOH (NaOH) of 75g/L 7% (w/w), the NaOH of 111g/L 10% (w/w), the NaOH of 162g/L 14% (w/w), the NaOH of 216g/L 18% (w/w) is in 25 ℃, slurries are handled (3% denseness, 15 minutes).Then slurry is washed removing NaOH, and copy the sheet machine by Formette Dynamique and form sheet material.Sheet material is carried out drying and utilizes the WileyMill grinder to grind, and is the flocculate of 0.39-0.49 millimeter thereby form number average flocculate length.
Method according to embodiment 1 changes into CMC with the cellulose wadding condensate.According to two CMC samples of cellulose wadding condensate preparation, and test.
According to identical cellulose slurry but NaOH of no use carries out mercerization to it handles preparation contrast cellulose wadding condensate.Also,, prepare CMC according to the method described in the embodiment 1 according to contrast cellulose wadding condensate.
The results are shown in Table 2.
Table 2
Mercerization is to the derive effect of the sheet material, flocculate and the CMC performance that obtain of SSK-
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples (0%) | 7％ | 10％ | 14％ | 18％ |
| Sheet material viscosity (cP) | 28.8 | 31.9 | 30.7 | 27.8 | 27.4 |
| Flocculate viscosity (cP) | 23.8 | 27.8 | 26.7 | 23.7 | 23.7 |
| Average floc length (mm) | 0.45 | 0.39 | 0.41 | 0.46 | 0.47 |
| Flocculate density (g/mL) | 0.149 | 0.166 | 0.187 | 0.180 | 0.194 |
| Flocculate WRVs (%) | 71.4 | 70.4 | 73.9 | 74.0 | 78.9 |
| Sheet material Rx value | 0.5505 | 0.5557 | 0.5925 | 0.6422 | 0.6516 |
| Sheet material cellulose II (%) | 0 | 0 | 24 | 61 | 72 |
| Sheet material crystallinity Xc (%) | 52 | 54 | 44 | 40 | 39 |
| CMC0.50% viscosity (cP) | 73 | 70 | 87 | 125 | 121 |
| CMC1% viscosity (cP) | 586 | 483 | 607 | 1268 | 1147 |
| CMC DS | 0.820 | 0.766 | 0.793 | 0.826 | 0.781 |
Compare with Comparative Examples, carry out the flocculate that mercerization is handled with 18% (w/w) NaOH, its dried bulk density will increase by 30%, and WRV will increase by 11%.Mercerization for 14% and 18% is handled, and the value added of viscosity (1.0%CMC solution) changes in 96% to 128% scope.For mercerization SSK slurry, the increase of this solution viscosity will enlarge the solution viscosity scope of the ether that is made by SSK greatly.
Handle for the mercerization of Comparative Examples and 18% (w/w), according to the degree of polymerization of following definite cellulose wadding condensate and CMC (weight average, DPw).According to Morton, J.H. at timber and sponge chemistry and processing (Kennedy, J.F., Phillips, G.O., Williams, P.A. edits, the 15th chapter, Woodhead Publishing Ltd., Cambridge, Eng.1996) the middle method of describing, the DPw of CED viscosity prediction cellulose wadding condensate by 0.5%.
According to being described in W.Brown, the method in the polymer chemistry of D.Henley and J.Oehman (62:164 (1963)) as solvent, is determined the Dpw of CMC with the cadmium hydroxide ethylenediamine solution by inherent viscosity.
The results are shown in following table 3.
Table 3
The DPw of CMC changes after the SSK naoh treatment
| Handle (w/wNaOH) | Cellulose wadding condensate viscosity (cP) | Cellulose wadding condensate DPw | CMC DPw | Etherification is with the change (%) of DPw |
| Comparative Examples (0%NaOH) | 23.8 | 2633 | 2270 | -14 |
| 18％NaOH | 23.7 | 2628 | 2605 | -1 |
During etherificate, comparative paste has demonstrated the reduction of DPw14%, and the mercerization flocculate only demonstrates 1% DPw reduction.
Embodiment 3
South softwood kraft pulp (SSK) derive the cellulose wadding condensate that obtains and the preparation of CMC
In chlorine dioxide, alkali treatment, ClO 2 bleaching section (DED) afterwards, (Foley, the dry SSK that do not have aborning that FL) produces starches, and carries out other laboratory scale bleaching by BuckeyeTechnolohies in collection.Then, utilize the NaOH of 75g/L 7% (w/w), the NaOH of 111g/L 10% (w/w), the NaOH of 162g/L 14% (w/w), the NaOH of 216g/L 18% (w/w) is in 25 ℃, slurries are handled (3% denseness, 15 minutes).Then slurry is washed to remove NaOH, handle, handle with sulfuric acid then with chlorine dioxide.With demineralized water the slurry that obtains is washed then, be lower than till 9, and copy sheet machine formation sheet material by Formette Dynamique until the pH of residual water.Utilizing Wiley Mill grinder that the sheet material of drying is ground, is the flocculate of 0.36-0.37 millimeter thereby form number average flocculate length (AFL).
According to the method for embodiment 1, the cellulose wadding condensate is changed into CMC.Independent two batch of materials of preparation CMC, and test according to each batch of material of the cellulose slurry of handling.
According to identical cellulose slurry but NaOH of no use carries out mercerization to it handles the preparation comparison.
The results are shown in Table 4.
Table 4
Mercerization is to the sheet material, flocculate and the CMC performance that do not have dry (ND) SSK-to derive to obtain
Effect
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples (0%) | 7％ | 10％ | 14％ | 18％ |
| Sheet material viscosity (cP) | 28.7 | 32.4 | 26.0 | 24.3 | 24.8 |
| Flocculate viscosity (cP) | 25.1 | 27.9 | 22.7 | 22.0 | 21.4 |
| Average floc length (mm) | 0.37 | 0.37 | 0.37 | 0.37 | 0.36 |
| Flocculate density (g/mL) | 0.205 | 0.179 | 0.224 | 0.242 | 0.233 |
| Flocculate WRVs (%) | 70.8 | 65.6 | 69.6 | 71.7 | 71.0 |
| Sheet material Rx value | 0.5439 | 0.5529 | 0.6085 | 0.6534 | 0.6659 |
| Sheet material cellulose II (%) | 0 | 0 | 39 | 69 | 74 |
| Sheet material crystallinity Xc (%) | 52 | 52 | 41 | 39 | 37 |
| CMC0.50% viscosity (cP) | 78 | 106 | 156 | 166 | 131 |
| CMC1% viscosity (cP) | 550 | 679 | 1108 | 1365 | 1472 |
| CMC DS | 0.869 | 0.831 | 0.806 | 0.802 | 0.820 |
Compare with Comparative Examples, the mercerization for 14% and 18% is handled, and 1.0%CMC viscosity in aqueous solution value added changes in 148% to 168% scope.Utilize 18% (w/w) NaOH to carry out the flocculate that mercerization is handled, its dried bulk density will be compared bigger by 14% than the dried bulk density of flocculate.
Embodiment 4
NSS derive the cellulose wadding condensate that obtains and the preparation of CMC
Utilization is set to 600 counter, according to the method for describing among the TAPPI TMI 73-06-00, non-mercerization north needlebush sulphite (NSS) pulpboard is decomposed, thereby form slurries.Then, utilize the NaOH (NaOH) of 75g/L 7% (w/w), the NaOH of 111g/L 10% (w/w), the NaOH of the NaOH of 162g/L 14% (w/w) and 18% (w/w) of 216g/L is in 25 ℃, slurries are handled (3% denseness, 15 minutes).Water washs slurry and with sulfuric acid and oxalic acid slurry is handled under 3.5% denseness then.Copying the sheet machine by Formette Dynamique and make slurry form sheet material, sheet material is carried out drying and utilizes Wiley Mill grinder to grind, is the cellulose wadding condensate of 0.28-0.29 millimeter thereby form number average flocculate length.Method according to embodiment 1 changes into CMC with flocculate.According to two independent CMC batch of materials of each preparing the batch of the cellulose paste of handling, and test.
By non-mercerization NSS sheet material directly being ground to form flocculate and this flocculate is changed into as described in example 1 above CMC, and prepare first Comparative Examples (Comparative Examples 1).
Utilization is set to 600 counter, according to the method for describing among the TAPPI TMI 73-06-00, makes non-mercerization NSS pulpboard be decomposed to form slurries, and prepares second Comparative Examples (Comparative Examples 2).Copy the sheet machine by Formette Dynamique and make the slurry of decomposition form sheet material, sheet material is carried out drying and utilizes Wiley Mill grinder to grind, thereby form the cellulose wadding condensate.As described in example 1 above, this flocculate is changed into CMC.
The results are shown in Table 5.
Table 5
Mercerization is to the derive effect of the sheet material, flocculate and the CMC performance that obtain of NSS-
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples 11 | Comparative Examples 12 | 7％ | 10％ | 14％ | 18％ |
| Sheet material viscosity (cP) | 67.2 | 60.0 | 64.8 | 63.6 | 65.4 | 61.9 |
| Flocculate viscosity (cP) | 47.4 | 56.1 | 51.0 | 53.7 | 52.5 | 49.8 |
| Average floc length (mm) | 0.29 | 0.27 | 0.28 | 0.28 | 0.27 | 0.29 |
| Flocculate density (g/mL) | 0.135 | 0.144 | 0.143 | 0.177 | 0.176 | 0.173 |
| Flocculate WRVs (%) | 74.7 | 70.2 | 68.1 | 73.0 | 75.8 | 73.1 |
| Sheet material Rx value | 0.5615 | 0.5365 | 0.5553 | 0.6129 | 0.6443 | 0.6438 |
| Sheet material cellulose II (%) | - | 0 | 0 | 40 | 61 | 65 |
| Sheet material crystallinity Xc (%) | - | 50 | 54 | 44 | 42 | 41 |
| CMC0.50% viscosity (cP) | 114 | 111 | 118 | 265 | 233 | 304 |
| CMC1% viscosity (cP) | 898 | 1087 | 853 | 2037 | 1835 | 2608 |
| CMC DS | 0.793 | 0.828 | 0.822 | 0.791 | 0.779 | 0.759 |
Compare with Comparative Examples, carry out the flocculate that mercerization is handled with 10,14 and 18% (w/w) NaOH, its dried bulk density all will have comparable increase (31-28%).The viscosity (1.0%CMC solution) of the CMC that utilizes 10,14 and 18% (w/w) to handle to make will be than the big 104-190% of Comparative Examples.Will be in the viscosity of this scope CMC solution greater than the viscosity of the commercially available prod of the CMC that makes by wood pulp.For mercerization NSS slurry, the increase of this solution viscosity will enlarge the range of viscosities of the ethereal solution that is made by NSS greatly.
Embodiment 5
SHK derive the cellulose wadding condensate that obtains and the preparation of CMC
Utilization is set to 600 counter, according to the method for describing among the TAPPI TMI 73-06-00, non-mercerization south leaf wood sulfate (SHK) pulpboard is decomposed, thereby form slurries.Then, utilize the NaOH (NaOH) of 75g/L 7% (w/w), the NaOH of 111g/L 10% (w/w), the NaOH of the NaOH of 162g/L 14% (w/w) and 18% (w/w) of 216g/L is in 25 ℃, slurries are handled (3% denseness, 15 minutes).Then slurry is washed and under 3.5% denseness, slurry is handled with sulfuric acid and oxalic acid.Copying the sheet machine by Formette Dynamique and make slurry form sheet material, sheet material is carried out drying and utilizes Wiley Mill grinder to grind, is the cellulose wadding condensate of 0.22-0.25 millimeter thereby form number average flocculate length.Method according to embodiment 1 changes into CMC with flocculate.According to two independent CMC batch of materials of each preparing the batch of the cellulose paste of handling, and test.
By non-mercerization SHK sheet material directly being ground to form flocculate and this flocculate is changed into as described in example 1 above CMC, and prepare first Comparative Examples (Comparative Examples 1).
Utilization is set to 600 counter, according to the method for describing among the TAPPI TMI 73-06-00, makes non-mercerization SHK pulpboard be decomposed to form slurries, and prepares second Comparative Examples (Comparative Examples 2).Copy the sheet machine by Formette Dynamique and make the slurry of decomposition form sheet material, sheet material is carried out drying and utilizes Wiley Mill grinder to grind, thereby form the cellulose wadding condensate.As described in example 1 above, this flocculate is changed into CMC.
The results are shown in Table 6.
Table 6
Mercerization is to the derive effect of the sheet material, flocculate and the CMC performance that obtain of SHK-
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples 11 | Comparative Examples 12 | 7％ | 10％ | 14％ | 18％ |
| Sheet material viscosity (cP) | 12.3 | 11.9 | 11.6 | 11.7 | 11.3 | 11.1 |
| Flocculate viscosity (cP) | 11.5 | 11.0 | 10.7 | 10.9 | 10.6 | 10.4 |
| Average floc length (mm) | 0.22 | 0.24 | 0.24 | 0.24 | 0.25 | 0.23 |
| Flocculate density (g/mL) | 0.135 | 0.120 | 0.125 | 0.140 | 0.138 | 0.132 |
| Flocculate WRVs (%) | 76.2 | 69.5 | 71.9 | 70.9 | 71.1 | 72.4 |
| Sheet material Rx value | 0.5629 | 0.5466 | 0.5699 | 0.5717 | 0.6290 | 0.6537 |
| Sheet material cellulose II (%) | - | 0 | 1 | 5 | 62 | 65 |
| Sheet material crystallinity Xc (%) | - | 53 | 52 | 49 | 37 | 39 |
| CMC0.50% viscosity (cP) | 49 | 65 | 48 | 71 | 148 | 143 |
| CMC1% viscosity (cP) | 230 | 362 | 251 | 461 | 547 | 923 |
| CMC DS | 0.805 | 0.728 | 0.790 | 0.701 | 0.634 | 0.659 |
During 100% to 18% amount of sodium hydroxide during from 10% amount of sodium hydroxide of the CMC solution for 1.0%, the viscosity value added of mercerized cellulose slurry 300%.
Embodiment 6
The dried flocculate density of the flocculate that will be made by the mercerization in embodiment 1,2 and 4 and non-mercerization cotton linter pulp, southern softwood kraft pulp and northern needlebush sulfite pulp is mapped in Fig. 1 to the average fiber length of flocculate respectively.
The percentage of NaOH is mapped in Fig. 2 during will being handled slurry by the Rx value of the mercerization cotton linter pulp that makes in embodiment 1,2,4 and 5, southern softwood kraft pulp, northern needlebush sulfite pulp and southern broad-leaved wood sulphate pulp respectively.
Embodiment 7
By there not being dry (wetting) CLP to prepare CMC
After boiling and bleaching, (Foley, the CLP (UVE level) that does not have drying aborning that FL) produces is used for laboratory scale mercerization by Buckeye Technolohies in collection.Then, utilize the NaOH of 216g/L 18% (w/w), do not handle (3% denseness, 15 minutes) having dry slurries.Treatment temperature is about 25 ℃.Then slurry is washed, and under 3.5% denseness, handle with sulfuric acid.Copying the sheet machine by Formette Dynamique and make slurry form sheet material, sheet material is carried out drying, and utilize Wiley Mill grinder that the sheet material of drying is ground, is the flocculate of 0.39-0.40 millimeter thereby form number average flocculate length.According to the method for embodiment 1, the cellulose wadding condensate is changed into CMC.
Prepare CMC by moistening, dry again finished product CLP
Utilization is set to 600 counter, according to TAPPI TMI 73-06-00, make from the drying of identical production route, finished product CLP sample decomposes, thereby forms slurries.As mentioned above, slurry is carried out mercerization handle, washing is handled with acid, forms sheet material, grinds to form flocculate, and changes into CMC.
The preparation (Comparative Examples) of dry finished product CLP
In order to compare, as mentioned above, collect the drying derive from identical production route, finished product CLP sample, grind to form flocculate and change into cellulose ether.
By each above-mentioned method three CMC samples of preparation and test.The results are shown in the following table 7.
Table 7
| Raw cellulose | Mercerization agent treating capacity (NaOH (w/w)) | Sample | Sheet material viscosity (cP) | Flocculate viscosity (cP) | Average floc length (mm) | The viscosity of CMC0.50% (cP) | The viscosity of CMC0.75% (cP) | The viscosity of CMC1.00% (cP) | CMC DS |
| Do not have dry wet pulp | 18％ | A | 227 | 188 | 0.39 | 1455 | 4695 | 76910 | 0.829 |
| 18％ | B | 227 | 188 | 0.39 | 1599 | 4856 | 80000 | 0.795 | |
| 18％ | C | 227 | 188 | 0.39 | 1658 | 5580 | 81320 | 0.800 | |
| - | Average | 227 | 188 | 0.39 | 1571 | 5044 | 79410 | 0.808 | |
| The CLP of moistening again drying | 18％ | A | 242 | 177 | 0.40 | 603 | 1891 | 29160 | 0.709 |
| 18％ | B | 242 | 177 | 0.40 | 708 | 2345 | 24010 | 0.772 | |
| 18％ | C | 242 | 177 | 0.40 | 1502 | 4436 | 77190 | 0.804 | |
| - | Average | 242 | 177 | 0.40 | 937 | 2891 | 43453 | 0.745 | |
| Comparative Examples | 0％ | A | 289 | 214 | 0.39 | 681 | 1992 | 19580 | 0.859 |
| 0％ | B | 289 | 214 | 0.39 | 746 | 2130 | 21370 | 0.755 | |
| 0％ | C | 289 | 214 | 0.39 | 708 | 2461 | 23530 | 0.822 | |
| - | Average | 289 | 214 | 0.39 | 712 | 2194 | 21493 | 0.812 |
The 1%CMC viscosity in aqueous solution that does not have dry mercerization CLP to provide will be higher by 296% than Comparative Examples.Before carried out the dry 1%CMC viscosity in aqueous solution that mercerization is handled of carrying out then, higher by 102% than Comparative Examples.
Embodiment 8
Prepare methylcellulose (MC) by finished product CLP
(Memphis, TN) the finished product CLP of Sheng Chaning (HVE level), and utilize and to be set to 600 counter decompose according to TAPPI TMI 73-06-00, thereby form slurries by Buckeye Technolohies cellulose factory in collection.Then, utilize the NaOH of 162g/L 14% (w/w), the NaOH of the NaOH of 216g/L 18% (w/w) and 24% (w/w) of 304g/L in 25 ℃, is handled (3% denseness, 15 minutes) to slurries.Then slurry is washed and under 3.5% denseness, handle with sulfuric acid and oxalic acid.Copying the sheet machine by FormetteDynamique and make slurry form sheet material, sheet material is carried out drying and utilizes Wiley Mill grinder to grind, is the flocculate of 0.29-0.31 millimeter thereby form number average flocculate length.
Utilize the high dense reactor of Drais, flocculate changed into MC by following, described reactor derive from Draiswerke GmbH (Mannheim, Germany).The cellulose wadding condensate (under blanket of nitrogen) of 150 grams (over dry) being purified with the NaOH of 296 grams 50% (w/w) sprays, and stirs 5 minutes at about 25 ℃.Then, with 374 gram chloromethanes (CH
3Cl) be added in the alkali cellulose.With the mixture heated that obtains to about 75 ℃ and reacted 2.5 hours.From reactor, take out the product that forms, and in 80 ℃ water, wash four times.Then, utilize compressed air that remaining MC is carried out drying at 105 ℃.
Utilize ASTM method D 3876-96, by Hewlett Packard gas-chromatography (5890 type), measure the substitution value (DS) of MC, wherein said chromatography has following chromatographic column: HewlettPackard HP-20M Carbowax 20M; 30M * 0.53mm * 1.33 μ m film thicknesses.
Utilize standard Brookfield viscosimeter (LVDV2+ type), according to following measurement ether rotary viscosity.MC is dissolved in hot water (80-90 ℃) and stirred 30 minutes.Then to this solution stirring and be cooled to 5 ℃.In water-bath with the adjustment to 20 of solution ℃, so that carry out viscosity measurement.
Determine the characteristic of other flocculate and ether by the method described in the embodiment 1.
According to two independent MC batch of materials of each preparing the batch of the cellulose slurry of handling, and test.
By identical method preparation contrast MC, different is that slurry is handled and washed without NaOH.
The results are shown in the following table 8.
Table 8
The sheet material that mercerization is derived and obtained CLP-, the effect of flocculate and MC
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples | 14％ | 18％ | 24％ |
| Sheet material viscosity (cP) | 307 | 223 | 211 | 218 |
| Flocculate viscosity (cP) | 182 | 160 | 158 | 179 |
| Average floc length (mm) | 0.31 | 0.30 | 0.31 | 0.29 |
| Flocculate density (g/mL) | 0.151 | 0.202 | 0.206 | 0.195 |
| Flocculate WRVs (%) | 57 | 67 | 67 | 62 |
| The viscosity of MC1% (cP) | 16347 | 176 | 86 | 76 |
| CMC DS | 2.02 | 1.92 | 1.85 | 1.65 |
Mercerization is handled and will be caused flocculate density and flocculate WRV to increase.The viscosity and the substitution value of the methylcellulose that is made by mercerization CLP will reduce with the increase of naoh concentration.
Embodiment 9
CLP derive the cellulose wadding condensate that obtains and the preparation of CMC
After boiling and bleaching, collect (Memphis, the CLP (UVE level) that does not have drying aborning that TN) produces by Buckeye Technolohies cellulose factory, utilize the NaOH of 216g/L 18% (w/w), in 25 ℃, slurries are handled (3% denseness, 15 minutes).Then slurry is washed and under 3.5% denseness, handle with sulfuric acid.Copying the sheet machine by FormetteDynamique and make slurry form sheet material, sheet material is carried out drying and utilizes Wiley Mill grinder to grind, is the flocculate of 0.40-0.41 millimeter thereby form number average flocculate length.
Utilize the high dense reactor of Drais, flocculate changed into CMC by following, described reactor derive from Draiswerke GmbH (Mannheim, Germany).The cellulose wadding condensate (under blanket of nitrogen) of 150 grams (over dry) being purified with the NaOH of 175 grams 50% (w/w) sprays, and stirs 60 minutes at about 25-30 ℃, so that form alkali cellulose.Then, the chloroacetic acid (MCA) that 102 grams are heated to 50 ℃, is dissolved in 99% (w/w) in the isopropyl alcohol is added in the alkali cellulose.Place the mixture that obtains under the blanket of nitrogen and be heated to about 70 ℃.With 70 ℃ of reactions 3.0 hours.After reaction stops, utilizing the B ü chner funnel of band #4 filter paper to make the mixture drainage.By from reactor, removing sodium chloride and accessory substance to the mixture washed twice with twice of methanol wash with aqueous methanol.Then, utilize compressed air that remaining CMC is carried out drying at 55 ℃.
According to two independent CMC batch of materials of each preparing the batch of the cellulose slurry of handling, and test.
In order to compare, will (Memphis, TN) the finished product CLP of Sheng Chaning (HVE level) sample directly grinds to form flocculate and changes into CMC by Buckeye Technolohies cellulose factory.
The results are shown in the following table 9.
Table 9
The sheet material that mercerization is derived and obtained CLP-, the effect of flocculate and MC
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples | 18％ |
| Sheet material viscosity (cP) | 330 | 222 |
| Flocculate viscosity (cP) | 208 | 171 |
| Average floc length (mm) | 0.41 | 0.40 |
| Flocculate density (g/mL) | 0.1025 | 0.1370 |
| CMC0.50% viscosity (cP) | 1422 | 2072 |
| CMC0.75% viscosity (cP) | 3125 | 5581 |
| CMC1.00% viscosity (cP) | 30145 | 75190 |
| CMC DS | 0.767 | 0.797 |
The density of the CLP flocculate of mercerization is greater than the density of non-mercerization CLP contrast flocculate.The CMC that is made by the mercerization fiber in the high-consistency reactor also demonstrates tangible increase (aqueous solution for 1% increases by 149%) aspect solution viscosity.
Embodiment 10
After boiling and bleaching, collect (Memphis, the CLP (UVE level) that does not have drying aborning that TN) produces by Buckeye Technolohies cellulose factory, utilize the NaOH of 216g/L 18% (w/w), in 25 ℃, slurries are handled (3% denseness, 15 minutes).Then slurry is washed and handle with sulfuric acid with 3.5% denseness.Copy the sheet machine by FormetteDynamique and make slurry form sheet material, to sheet material carry out dry until slurry drying to over dry or have 30% moisture content.Utilizing Wiley Mill grinder that sheet material is ground, is the flocculate of 0.38-0.41 millimeter thereby form number average flocculate length.
Method according to described in the embodiment 1 makes flocculate change into CMC.Change the addition of water according to the moisture content of slurry, to guarantee that water and cellulosic ratios constant were at about 2.6: 1.
According to two independent CMC batch of materials of each preparing the batch of the cellulose slurry of handling, and test.
In order to compare, as mentioned above, the same sample that does not have dry CLP is aborning tested, different is to carry out the mercerization processing by 18% (w/w) NaOH.
The results are shown in the following table 10.
Table 10
The sheet material of mercerization to not having dry CLP-to derive and obtain, the effect of flocculate and CMC
| Mercerization agent treating capacity (NaOH (w/w)) | Comparative Examples (0%) | Comparative Examples (0%) | 18％ | 18％ |
| Sheet material water content (%w/w) | Over dry | 30 | Over dry | 30 |
| Sheet material viscosity (cP) | 325 | 298 | 219 | 205 |
| Flocculate viscosity (cP) | 249 | 260 | 185 | 173 |
| Wadding average floc length (mm) | 0.38 | 0.39 | 0.41 | 0.40 |
| CMC0.50% viscosity (cP) | 615 | 616 | 1180 | 1332 |
| CMC0.75% viscosity (cP) | 2113 | 1944 | 3506 | 3505 |
| CMC1.00% viscosity (cP) | 25685 | 13920 | 55335 | 57190 |
| CMC DS | 0.827 | 0.830 | 0.787 | 0.791 |
For the CLP of over dry or 30% moisture content, 18% NaOH mercerization is handled all will increase the CMC1% viscosity in aqueous solution.
Embodiment 11
Utilize Wiley Mill grinder, will (Memphis, TN) the finished product CLP of Sheng Chaning (HVE level) grinds to form flocculate (its average floc length is 0.39mm) by Buckeye Technolohies cellulose factory.Utilize the NaOH of 216g/L 18% (w/w),, the flocculate that obtains is carried out mercerization handle (3% denseness, 15 minutes) in 25 ℃.Water washs flocculate and handles with sulfuric acid and oxalic acid with 3.5% denseness then.With the different time, in 71 ℃ baking oven, flocculate is carried out drying.According to the method described in the embodiment 1, flocculate is changed into CMC then.Change the addition of water according to the moisture content of slurry, to guarantee that water and cellulosic ratios constant were at about 2.6: 1.
According to two independent CMC batch of materials of each preparing the batch of the cellulose slurry of handling, and test.
In order to compare, as mentioned above, CMC is derived by identical flocculate and obtains, and different is to carry out the mercerization processing by 18% (w/w) NaOH.
The results are shown in the following table 11.
Table 11
| Flocculate mercerization amount (%NaOH) | Flocculate water content (%w/w) | Flocculate viscosity (cP) | CMC viscosity 0.5% (cP) | CMC viscosity 1.0% (cP) | CMC DS |
| 18 | 53 | 152 | 915 | 6217 | 0.765 |
| 18 | 39 | 158 | 1107 | 6414 | 0.744 |
| 18 | 9 | 163 | 1002 | 6376 | 0.752 |
| Comparative Examples | 7 | 195 | 524 | 5440 | 0.795 |
Embodiment 12
To test finished product slurry sample (being SSK, NSS, SHK and CLP) according to following as embodiment 2,4,5 and 11.Each sample is cut into bar.Then, in liquefied ammonia is bathed, each bar is carried out mercerization and handled 30 minutes, so that form cellulose III in-50 ℃.Then in 105 ℃ baking oven with the bar dried overnight of mercerization.Utilize the WileyMill grinder that bar is ground, to form flocculate.According to the method described in the embodiment 1 flocculate is changed into CMC.Prepare two CMC batch of materials, and test according to processing and cellulosic type.
As a comparison case, prepare CMC by said sample, different sample carry out mercerization without liquefied ammonia and handle.The results are shown in the following table 12.
Table 12
| Cellulose kind/processing | Sheet material viscosity (cP) | Flocculate viscosity (cP) | Average floc length (mm) | Flocculate density (g/mL) | Flocculate WRVs (%) | CMC viscosity 0.50% (cP) | CMC viscosity 1.0% (cP) | CMC DS |
| The CLP/ contrast | 319 | 200 | 0.37 | 0.1188 | 59.2 | 451 | 4158 | 0.859 |
| CLP/ ammonia | 232 | 196 | 0.38 | 0.1139 | 55.6 | 473 | 3899 | 0.857 |
| The SHK/ contrast | 12 | 12 | 0.34 | 0.0885 | 77.0 | 42 | 184 | 0.870 |
| SHK/ ammonia | 11 | 10 | 0.33 | 0.0993 | 64.3 | 38 | 159 | 0.820 |
| The SSK/ contrast | 28 | 26 | 0.42 | 0.1763 | 77.3 | 67 | 471 | 0.835 |
| SSK/ ammonia | 20 | 19 | 0.41 | 0.1815 | 75.7 | 64 | 385 | 0.808 |
| The NSS/ contrast | 64 | 59 | 0.39 | 0.0965 | 77.3 | 99 | 702 | 0.864 |
| NSS/ ammonia | 44 | 40 | 0.39 | 0.1079 | 75.7 | 99 | 711 | 0.846 |
Embodiment 13
To test finished product slurry sample (being SSK and CLP) according to following as embodiment 2 and 11.Each sample is cut into bar.Then, in the mixture of liquefied ammonia (1700mL) and methyl alcohol (300mL), each bar is carried out mercerization handled 5 minutes in-Yue 35 ℃, so that form cellulose III.Then in fume hood, make air-dry 72 hours of the bar of mercerization.Utilize Wiley Mill grinder that bar is ground, to form flocculate.According to the method described in the embodiment 1 flocculate is changed into CMC.Prepare two CMC batch of materials, and test according to processing and cellulosic type.
As a comparison case, prepare CMC by said sample, different sample carry out mercerization without liquefied ammonia and handle.The results are shown in the following table 13.
Table 13
| The mercerization agent is handled | CLP | SSK | ||
| Comparative Examples | Ammonia | Comparative Examples | Ammonia | |
| Sheet material viscosity (cP) | 356 | 277 | 28 | 27 |
| Flocculate viscosity (cP) | 216 | 239 | 26 | 25 |
| Average floc length (mm) | 0.40 | 0.41 | 0.43 | 0.41 |
| Flocculate density (g/mL) | 0.101 | 0.091 | 0.144 | 0.153 |
| CMC0.50% viscosity (cP) | 727 | 478 | 70 | 55 |
| CMC1% viscosity (cP) | 5134 | 4135 | 404 | 316 |
| CMC DS | 0.839 | 0.848 | 0.852 | 0.860 |
At this all lists of references of quoting as proof are incorporated herein by reference.Between specification and list of references, may exist to a certain degree conflict at this language as contrast.
Claims (62)
1. the preparation method of a cellulose ether comprises the steps:
(a) obtain mercerization and the cellulose slurry that reclaims and
(b) make the cellulose slurry of mercerization and recovery change into cellulose ether,
Wherein using cellulose II mercerization agent that the cellulose paste of the mercerization in the step (a) is carried out mercerization handles, wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, and wherein said recovery comprises neutralization and/or washing.
2. the process of claim 1 wherein that when cellulose slurry is southern softwood kraft pulp the TAPPI 230 om-89 viscosity numbers of the cellulose slurry of mercerization and recovery are greater than 12cP.
3. the process of claim 1 wherein that described cellulose slurry is selected from: cotton linter pulp, the plain slurry of broad-leaved wood fiber, the plain slurry of needle-leaved wood fibre, sulfite cellulose slurry, sulphate cellulose slurry, rehydration cellulose slurry and aforementioned combination arbitrarily.
4. the method for claim 3, wherein the plain slurry of broad-leaved wood fiber is selected from: southern hemisphere leaf wood sulphate cellulose slurry, south hemisphere leaf wood sulfite cellulose slurry, this may be starched by ground Na Weiya leaf wood sulphate cellulose, this may be starched by ground Na Weiya leaf wood sulfite cellulose, north leaf wood sulphate cellulose slurry, north leaf wood sulfite cellulose slurry, south leaf wood sulphate cellulose slurry, south leaf wood sulfite cellulose slurry, torrid zone leaf wood sulphate cellulose slurry, torrid zone leaf wood sulfite cellulose slurry, and aforesaid any combination.
5. the method for claim 3, wherein, the plain slurry of needle-leaved wood fibre is selected from: southern hemisphere needlebush sulphate cellulose slurry, southern hemisphere needlebush sulfite cellulose slurry, this may ground Na Weiya needlebush sulphate cellulose slurry, this may ground Na Weiya needlebush sulfite cellulose slurry, southern needlebush sulphate cellulose slurry, northern needlebush sulphate cellulose slurry, southern needlebush sulfite cellulose slurry, northern needlebush sulfite cellulose slurry and aforesaid any combination.
6. the method for claim 3, wherein the sulfite cellulose slurry is selected from: southern needlebush sulfite cellulose slurry, northern needlebush sulfite cellulose slurry, tropical leaf wood sulfite cellulose slurry and aforementioned combination arbitrarily.
7. the process of claim 1 wherein that cellulose slurry is a cotton linter pulp.
8. the process of claim 1 wherein that cellulose slurry is a needlebush sulfite cellulose slurry.
9. the process of claim 1 wherein that cellulose slurry is not have dry cellulose slurry.
10. the process of claim 1 wherein that cellulose slurry is non-regenerated cellulose slurry.
11. the process of claim 1 wherein that mercerization and the cellulose slurry that reclaims are the cellulose wadding condensates.
12. the step of the process of claim 1 wherein (a) comprising:
(i) make the cellulose slurry mercerization and
(ii) wash, neutralize or wash and in and mercerized cellulose slurry.
13. the step of the process of claim 1 wherein (a) comprising:
(i) make the cellulose slurry mercerization and
(ii) wash the mercerized cellulose slurry.
14. the method for claim 13 is wherein washed the mercerized cellulose slurry of step (a) in (ii) with the aqueous solution.
15. the method for claim 14, wherein the washing step pH that is performed until residual water is lower than till 10.
16. the method for claim 12, wherein step (a) comprises also that in addition cellulose slurry that (iii) mercerization is also washed, neutralization or washing and neutralization carries out drying.
17. the method for claim 16, wherein mercerization and dry cellulose slurry comprise the moisture content that is lower than 20% weight in plain slurry of total fiber and water 100% weight.
18. the method for claim 11, wherein step (a) comprising:
(i) cellulose slurry is processed into the cellulose wadding condensate;
(ii) the cellulose wadding condensate being carried out mercerization handles; With
(iii) wash, neutralize or neutralize and wash the cellulose wadding condensate of mercerization.
19. the cellulose slurry that the process of claim 1 wherein mercerization and reclaim is cellulose III not.
20. the process of claim 1 wherein that mercerization and the cellulose slurry that reclaims comprise the mercerization agent that is lower than 0.3% weight in cellulose slurry and mercerization agent 100% weight.
21. the method for claim 20, wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 0.03% weight in cellulose slurry and mercerization agent 100% weight.
22. the Rx value of the cellulose slurry that the process of claim 1 wherein mercerization and reclaim is greater than 0.57.
23. the method for claim 22, wherein the Rx value of the cellulose slurry of mercerization and recovery is greater than 0.60.
24. the method for claim 23, wherein the Rx value of the cellulose slurry of mercerization and recovery is greater than 0.64.
25. the cellulose slurry that the process of claim 1 wherein mercerization and reclaim comprises the cellulose II of at least 20% weight in the gross weight of mercerized cellulose slurry crystalline portion 100%.
26. the cellulose slurry that the process of claim 1 wherein mercerization and reclaim has the degree of crystallinity that is lower than 60% weight in the plain slurry of total fiber 100% weight.
27. the step of the process of claim 1 wherein (b) comprises by cellulose wadding condensate intermediate the mercerized cellulose slurry is changed into cellulose ether.
28. the method for claim 27, wherein step (b) comprising:
(i) cellulose slurry with mercerization and recovery is processed into the cellulose wadding condensate;
(ii) the cellulose wadding condensate is alkalized into alkali cellulose; With
(iii) the alkali cellulose etherificate is become cellulose ether.
29. the method for claim 28, wherein step (b) (i) comprises mercerized cellulose slurry is ground, shreds or shears, so that formation cellulose wadding condensate.
30. the method for claim 28, wherein step (b) (ii) comprises with basifier the cellulose wadding condensate is handled.
31. the method for claim 30, wherein basifier is an alkali metal hydroxide.
32. the method for claim 28, wherein step (b) (iii) comprises with etherifying agent alkali cellulose is handled, to form cellulose ether.
33. the method for claim 32, wherein etherifying agent comprises chloroacetic acid sodium.
34. the method for claim 11, wherein step (b) comprising:
(i) the cellulose wadding condensate is alkalized into alkali cellulose; With
The cellulose ether that (ii) will alkalize changes into cellulose ether.
35. the process of claim 1 wherein that cellulose ether is a carboxymethyl cellulose.
36. the process of claim 1 wherein that cellulose ether is a methylcellulose.
37. the process of claim 1 wherein that cellulose ether is a nonionic ether.
38. the process of claim 1 wherein that cellulose ether is an ion ether.
39. TYLOSE 30000 that makes by the method for claim 35.
40. methyl cellulose ether that makes by the method for claim 36.
41. nonionic cellulose ether that makes by the method for claim 37.
42. plain ether of ion fiber that makes by the method for claim 38.
43. the preparation method of a cellulose wadding condensate comprises the steps:
(a) obtain mercerization and the cellulose slurry that reclaims and
(b) cellulose slurry of mercerization is handled with formation cellulose wadding condensate,
Mercerization and the cellulose slurry that reclaims cellulose III not wherein, and wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.
44. the method for claim 43, wherein when cellulose slurry was southern softwood kraft pulp, the TAPPI 230 om-89 viscosity numbers of the cellulose slurry of mercerization and recovery will be greater than 12cP.
45. the method for claim 43, wherein, cellulose slurry is selected from: cotton linter pulp, the plain slurry of broad-leaved wood fiber, the plain slurry of needle-leaved wood fibre, sulfite cellulose slurry, sulphate cellulose slurry, rehydration cellulose slurry and aforesaid any combination.
46. the method for claim 43, wherein cellulose slurry is the sulfite cellulose slurry.
47. the method for claim 43, wherein step (a) comprising:
(i) make the cellulose slurry mercerization; With
(ii) the mercerized cellulose slurry is washed, neutralizes or neutralize and washs.
48. the method for claim 43, wherein, in cellulose slurry and mercerization agent 100% gross weight, described mercerization and the cellulose slurry that reclaims comprise the mercerization agent that is lower than 0.3% weight.
49. the preparation method of a mercerized cellulose flocculate comprises the steps:
(a) make the mercerization of cellulose wadding condensate; With
(b) reclaim the mercerized cellulose flocculate,
Wherein, the cellulose wadding condensate of mercerization and recovery is cellulose III not, and wherein the cellulose wadding condensate of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose wadding condensate and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.
50. the cellulose ether that the cellulose slurry that is also reclaimed by mercerization obtains, wherein the cellulose slurry of mercerization and recovery comprises the cellulose II of at least 20% weight in the gross weight of mercerized cellulose slurry crystalline portion 100%, and wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.
51. the cellulose ether of claim 50, wherein the cellulose slurry of mercerization and recovery comprises the cellulose II of at least 35% weight in the gross weight of mercerized cellulose slurry crystalline portion 100%.
52. the cellulose ether of claim 51, wherein the cellulose slurry of mercerization and recovery comprises the cellulose II of at least 60% weight in the gross weight of mercerized cellulose slurry crystalline portion 100%.
53. the cellulose ether that the cellulose slurry that is also reclaimed by mercerization obtains, wherein the Rx value of the cellulose slurry of mercerization and recovery is greater than 0.57, and wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.
54. the cellulose ether of claim 53, wherein the Rx value of the cellulose slurry of mercerization and recovery is greater than 0.60.
55. the cellulose ether of claim 54, wherein the Rx value of the cellulose slurry of mercerization and recovery is greater than 0.64.
56. the cellulose ether that the cellulose slurry that is also reclaimed by mercerization obtains, wherein the cellulose slurry of mercerization and recovery has the degree of crystallinity that is lower than 60% weight in the plain slurry of total fiber 100% weight, and wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose slurry and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.
57. the cellulose ether of claim 56, wherein the cellulose slurry of mercerization and recovery has the degree of crystallinity that is lower than 45% weight in the plain slurry of total fiber 100% weight.
58. the cellulose ether that the cellulose slurry that is also reclaimed by mercerization obtains, wherein the cellulose slurry of mercerization and recovery comprises the moisture content that is lower than 20% weight in cellulose slurry 100% gross weight of mercerization and recovery, and wherein the cellulose slurry of mercerization and recovery comprises the mercerization agent that is lower than 3.5% weight in cellulose oar and mercerization agent 100% weight, wherein said mercerization agent is cellulose II mercerization agent, and described recovery comprises neutralization and/or washing.
59. the cellulose ether of claim 50 or 53, wherein said cellulose ether are ion fiber element ether or nonionic cellulose ether.
60. the cellulose ether of claim 59, wherein said cellulose ether are carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylcellulose or methylhydroxypropylcellulose.
61. the cellulose ether of claim 60, wherein said cellulose ether is a carboxymethyl cellulose.
62. the cellulose ether of claim 60, wherein said cellulose ether is a hydroxyethylcellulose.
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| US9926385B2 (en) * | 2013-08-12 | 2018-03-27 | Shin-Etsu Chemical Co., Ltd. | Method for producing water-soluble cellulose ether having low degree of polymerization and method for producing film coating composition comprising same |
| CN103911908A (en) * | 2014-03-20 | 2014-07-09 | 杭州特种纸业有限公司 | Air filter paper |
| US9771687B2 (en) * | 2016-02-25 | 2017-09-26 | International Paper Company | Crosslinked cellulose as precursor in production of high-grade cellulose derivatives and related technology |
| CA3040734A1 (en) | 2016-11-16 | 2018-05-24 | Gp Cellulose Gmbh | Modified cellulose from chemical fiber and methods of making and using the same |
| US10980747B2 (en) * | 2017-11-27 | 2021-04-20 | Shin-Etsu Chemical Co., Ltd. | Composition for solid preparation, solid preparation, and method for producing the same |
| JP6983139B2 (en) * | 2017-11-27 | 2021-12-17 | 信越化学工業株式会社 | Compositions for solid formulations, solid formulations and methods for producing them |
| JP7323515B2 (en) * | 2018-05-29 | 2023-08-08 | 日本製紙株式会社 | Paper containing carboxymethylated cellulose |
| KR20200140196A (en) * | 2019-06-05 | 2020-12-15 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Pulverized pulp and method of producing cellulose ether using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2687352A (en) * | 1946-02-21 | 1954-08-24 | Brown Co | Process of refining hardwood pulp |
| US2636879A (en) * | 1950-04-27 | 1953-04-28 | Du Pont | Manufacture of cellulose ethers |
| SE403782B (en) * | 1973-03-14 | 1978-09-04 | Mo Och Domsjoe Ab | NONJONIC CELLULOSEETERS |
| US4063018A (en) * | 1975-04-07 | 1977-12-13 | Daicel Ltd. | Process for preparing alkali metal salt of carboxymethyl cellulose ether |
| DE2929002A1 (en) * | 1979-07-18 | 1981-02-12 | Henkel Kgaa | METHOD FOR PRODUCING CELLULOSE DERIVATIVES BY MEANS OF PARTICULARLY REACTIVE ALKALICELLULOSE |
| DE3216786A1 (en) * | 1982-05-05 | 1983-11-10 | Wolff Walsrode Ag, 3030 Walsrode | METHOD FOR PRODUCING HYDROXYALKYLMETHYLCELLULOS |
| SE463313B (en) * | 1989-03-10 | 1990-11-05 | Berol Nobel Stenungssund Ab | WATER-SOLUBLE, NON-NONIC CELLULOSETERS AND THEIR APPLICATION IN MAIL ARRIVALS |
| JP3002916B2 (en) * | 1991-10-29 | 2000-01-24 | ダイセル化学工業株式会社 | Production method of cellulose mixed ether |
| DE4203529A1 (en) * | 1992-02-07 | 1993-08-12 | Wolff Walsrode Ag | WATER-SOLUBLE SULFOALKYL HYDROXYALKYL DERIVATIVES OF CELLULOSE AND THEIR USE IN PLASTER AND CEMENT CONTAINERS |
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2000
- 2000-04-26 JP JP2000613873A patent/JP2003518145A/en active Pending
- 2000-04-26 CN CN00807877.7A patent/CN1239780C/en not_active Expired - Fee Related
- 2000-04-26 AU AU48040/00A patent/AU4804000A/en not_active Abandoned
- 2000-04-26 AT AT00930174T patent/ATE332997T1/en not_active IP Right Cessation
- 2000-04-26 BR BR0011214-3A patent/BR0011214A/en not_active Application Discontinuation
- 2000-04-26 MX MXPA01010897A patent/MXPA01010897A/en unknown
- 2000-04-26 CA CA2371815A patent/CA2371815C/en not_active Expired - Fee Related
- 2000-04-26 DE DE60029337T patent/DE60029337T2/en not_active Expired - Lifetime
- 2000-04-26 WO PCT/US2000/011283 patent/WO2000065145A1/en active IP Right Grant
- 2000-04-26 EP EP00930174A patent/EP1230456B1/en not_active Expired - Lifetime
- 2000-04-27 AR ARP000102012A patent/AR023782A1/en active IP Right Grant
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Also Published As
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| EP1230456A1 (en) | 2002-08-14 |
| ATE332997T1 (en) | 2006-08-15 |
| AR023782A1 (en) | 2002-09-04 |
| NO20015196D0 (en) | 2001-10-24 |
| BR0011214A (en) | 2002-12-17 |
| CA2371815C (en) | 2010-05-25 |
| AU4804000A (en) | 2000-11-10 |
| CN1360651A (en) | 2002-07-24 |
| DE60029337T2 (en) | 2007-07-05 |
| JP2003518145A (en) | 2003-06-03 |
| DE60029337D1 (en) | 2006-08-24 |
| MXPA01010897A (en) | 2002-11-07 |
| EP1230456B1 (en) | 2006-07-12 |
| CA2371815A1 (en) | 2000-11-02 |
| WO2000065145A1 (en) | 2000-11-02 |
| NO20015196L (en) | 2001-12-27 |
| EP1230456A4 (en) | 2002-08-14 |
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